EP3363849A1 - Polyolefin resin powder for selective laser sintering and preparation method therefor - Google Patents
Polyolefin resin powder for selective laser sintering and preparation method therefor Download PDFInfo
- Publication number
- EP3363849A1 EP3363849A1 EP16854740.4A EP16854740A EP3363849A1 EP 3363849 A1 EP3363849 A1 EP 3363849A1 EP 16854740 A EP16854740 A EP 16854740A EP 3363849 A1 EP3363849 A1 EP 3363849A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- parts
- polyolefin resin
- autoclave
- mpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 161
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 87
- 238000000110 selective laser sintering Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title description 4
- 239000002245 particle Substances 0.000 claims abstract description 113
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000009826 distribution Methods 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- -1 polypropylene Polymers 0.000 claims description 91
- 239000004743 Polypropylene Substances 0.000 claims description 80
- 229920001155 polypropylene Polymers 0.000 claims description 80
- 229920013716 polyethylene resin Polymers 0.000 claims description 66
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 64
- 229920005989 resin Polymers 0.000 claims description 63
- 239000011347 resin Substances 0.000 claims description 63
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 40
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 40
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 13
- 235000013539 calcium stearate Nutrition 0.000 claims description 13
- 239000008116 calcium stearate Substances 0.000 claims description 13
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 11
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 10
- 239000003242 anti bacterial agent Substances 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 239000002667 nucleating agent Substances 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- ZISSAWUMDACLOM-UHFFFAOYSA-N triptane Chemical compound CC(C)C(C)(C)C ZISSAWUMDACLOM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 claims description 6
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002216 antistatic agent Substances 0.000 claims description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002671 adjuvant Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 claims description 4
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2-dimethylpentane Chemical compound CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 claims description 4
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 claims description 4
- AORMDLNPRGXHHL-UHFFFAOYSA-N 3-ethylpentane Chemical compound CCC(CC)CC AORMDLNPRGXHHL-UHFFFAOYSA-N 0.000 claims description 4
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 claims description 4
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229940092690 barium sulfate Drugs 0.000 claims 2
- 229960003563 calcium carbonate Drugs 0.000 claims 2
- 229940087373 calcium oxide Drugs 0.000 claims 1
- 229940105289 carbon black Drugs 0.000 claims 1
- 229960000829 kaolin Drugs 0.000 claims 1
- 229940043356 mica Drugs 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 229910001873 dinitrogen Inorganic materials 0.000 description 38
- 238000001291 vacuum drying Methods 0.000 description 38
- 239000000498 cooling water Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 17
- 238000000149 argon plasma sintering Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 229920000098 polyolefin Polymers 0.000 description 14
- 230000008569 process Effects 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- RZTYEUCBTNJJIW-UHFFFAOYSA-K silver;zirconium(4+);phosphate Chemical compound [Zr+4].[Ag+].[O-]P([O-])([O-])=O RZTYEUCBTNJJIW-UHFFFAOYSA-K 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- 239000004711 Ī±-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/007—Treatment of sinter powders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Definitions
- the present invention relates to the technical field of polymer processing, in particular to a method for preparing a polyolefin resin powder and a polyolefin resin powder obtained thereby and its use for selective laser sintering.
- SLS Selective Laser Sintering
- the SLS technology is a method in which a computer first scans a three-dimensional solid article, and then high-strength laser light is used to irradiate material powders pre-spreading on a workbench or a component, and selectively melt-sinter it layer-by-layer, thereby realizing a layer-by-layer molding technology.
- the SLS technology has a high degree of design flexibility, is capable of producing accurate models and prototypes, and is capable of molding components that have reliable structure and can be used directly.
- the types of molding materials that can be used for the SLS technology are relatively extensive, such as polymers, paraffins, metals, ceramics, and their composites.
- the performances and properties of molding materials are one of the essential factors to successful sintering of the SLS technology, because they directly affect the molding speed, precision, physical and chemical properties and overall performance of molded parts.
- the polymer powdery raw materials that can be directly applied to the SLS technology for successfully manufacturing molded products with small dimensional deviations, good surface regularity, and low porosity are rarely seen in the market. Therefore, it is urgent to develop and improve the polymer types applicable to the SLS technology and their corresponding solid powdery raw materials.
- a pulverization method such as a cryogenic pulverization method is generally used to prepare powdery raw materials suitable for the SLS.
- a cryogenic pulverization method is disclosed in CN104031319A .
- this method requires a specific equipment.
- the surface of the prepared powdery raw material particle is rough, the particle size is not uniform enough, and the shape is irregular, which is not conducive to the formation of sintered molded body and affects the performance of the molded body.
- a precipitation method may be used to prepare polymer powdery raw materials, such as polyamide powders.
- the polyamide is usually dissolved in a suitable solvent, uniformly dispersed in the solvent by stirring, and then the powders are precipitated upon cooling.
- CN103374223A discloses a precipitation polymer powder based on an AABB-type polyamide, which is obtained by reprecipitating a polyamide formed by polycondensation of a diamine and a dicarboxylic acid.
- alcoholic solvents are used during reprecipitation.
- a first aspect of the present invention is to provide a polyolefin resin powder and a preparation method thereof and its use for selective laser sintering.
- the polyolefin resin powder provided according to the present invention has good oxidation resistance, good powder flowability, moderate size, suitable bulk density, well-proportioned particle shape and uniform particle size distribution, which is particularly suitable for selective laser sintering to prepare various molded articles.
- the method for preparing a polyolefin resin powder according to the present invention includes the following steps:
- a second aspect of the present invention lies in a polyolefin resin powder obtained according to the method of the present invention.
- a third aspect of the present invention lies in a selective laser sintering method.
- a fourth aspect of the present invention lies in use of a polyolefin resin powder obtained according to the method of the present invention in a method of producing a three-dimensional object.
- a suitable polyolefin in the preparation method of the polyolefin resin powder according to the present invention, there is no particular limitation on a suitable polyolefin as long as it can be made in the form of a powder material.
- Polyolefins suitable for use in the method of the present invention may be selected from polymers which are obtained by polymerizing or copolymerizing linear, branched or cyclic olefins, e.g. C 2 -C 10 olefins, preferably ā -olefins, or mixtures of these polymers.
- Suitable olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and the like.
- the polyolefin is selected from polypropylene (PP) and polyethylene (PE) or mixtures thereof. More preferably, the polyolefin is one of polypropylene or polyethylene.
- the polypropylene is at least one selected from the group consisting of homopolypropylene resin and atactic polypropylene resin.
- the homopolypropylene resin has an isotacticity of ā 95%, for example 95-98%; and the atactic polypropylene resin has an isotacticity of ā 95%, for example 91-94.5%.
- the homopolypropylene resin and the atactic polypropylene resin have a melt index, measured at 210Ā°C and a load of 2.16 kg, of 20-100 g/10 min, preferably 30-80 g/10 min.
- the polyethylene resin has a density of ā 0.900 g/cm 3 , preferably 0.910-0.990 g/cm 3 ; a melt index, measured at 190Ā°C and a load of 2.16 kg, of 20-100 g/10 min, preferably 30-80 g/10 min. Within these ranges, the polyolefin resin exhibits good flowability, which is advantageous to the laser sintering process.
- the organic solvent is selected to have a solubility parameter less than or equal to the solubility parameter of the polyolefin resin, and the difference is within 0-20%, preferably within 0-15%, for example, within 0-12% of the solubility parameter of the polyolefin resin.
- the solvent is further selected to be a low boiling solvent.
- the term "low boiling (solvent)" means that the solvent has a boiling point of no more than 160Ā°C, such as no more than 150Ā°C or 130Ā°C, at normal pressure.
- the organic solvent is used in an amount of 600-1200 parts by weight, preferably 800-1000 parts by weight, based on 100 parts by weight of the polyolefin resin. When the organic solvent is used in an amount within this range, a polyolefin resin powder having good morphology and dispersibility can be obtained.
- the organic solvent is selected from C 5 -C 12 alkanes, preferably C 5 -C 9 alkanes, more preferably at least one selected from the group consisting of n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, n-octane, and n-nonane.
- n-pentane isopentane
- n-hexane 2-methylpentane
- 2-methylpentane 3-methylpentane
- the organic solvent is selected from C 6 -C 8 alkanes such as n-hexane, n-heptane and/or n-octane.
- the inventors of the present invention have further found through extensive experiments that when using the above organic solvents, particularly n-hexane and/or n-heptane, to dissolve the polyolefin resin and cooling to precipitate, the polyolefin resin can precipitate in a spherical and/or spheroidal shape, with a particle size of 25-150 ā m.
- the obtained polyolefin resin powder has smooth surface, good dispersibility and small size distribution, and is particularly suitable for selective laser sintering technology.
- the polyolefin resin is advantageously heated to a temperature of 60-200Ā°C, e.g., 70-190Ā°C or 80-160Ā°C.
- polypropylene resin is heated to 90-180Ā°C, preferably 100-150Ā°C, more preferably 110-140Ā°C.
- polyethylene resin is heated to 70-150Ā°C, preferably 80-130Ā°C, more preferably 90-110Ā°C.
- the polyolefin resin solution may be held at said heating temperature for 30-90 minutes for sufficient dissolution.
- the dissolution of step a) and the reprecipitation of step b) are advantageously carried out under pressure.
- the pressure can be established by vapor pressure of a solvent in a closed system.
- a nucleating agent may optionally be added in step a).
- Said nucleating agent is at least one selected from the group consisting of silica, calcium oxide, calcium carbonate, barium sulfate, hydrotalcite, talc, carbon black, kaolin and mica.
- the nucleating agent may be used in an amount of 0.01-2 parts by weight, preferably 0.05-1 parts by weight, and more preferably 0.1-0.5 parts by weight, based on 100 parts by weight of the polyolefin resin.
- the inventors of the present invention have found in experiments that, when these nucleating agents are added, the crystallization rate of the polyolefin resin can be increased, and the surface smoothness, heat resistance, and mechanical properties of the obtained polyolefin powder can be improved.
- a nucleating agent is used in the case when a polypropylene resin powder is used as the polyolefin resin.
- the average cooling rate is 0.1Ā°C/min to 1Ā°C/min.
- the polyolefin resin solution is preferably cooled down to a target temperature and held at the target temperature for 30-90 minutes, wherein the target temperature is preferably 10-30Ā°C, for example, room temperature (i.e., about 25Ā°C).
- the cooling of the polyolefin resin solution can be performed at a uniform rate in one step, or it can be performed in a stepwise manner.
- the polyolefin resin solution is cooled to a target temperature via one or more intermediate temperatures and held at said intermediate temperatures for 30-90 minutes, said intermediate temperatures being in the range of 40-100Ā°C, for example, 50-90Ā°C.
- the intermediate temperature is preferably 60-100Ā°C, more preferably 70-90Ā°C; for polyethylene, the intermediate temperature is preferably 40-80Ā°C, more preferably 50-70Ā°C. This will bring out a better precipitation effect.
- the intermediate temperature refers to the temperature between the heating temperature of step a) and the target temperature of step b).
- a homopolyolefin (e.g., homopolypropylene) resin solution can be cooled from a heating temperature of 130Ā°C to 90Ā°C and held at 90Ā°C for 60 minutes, and then cooled down to room temperature; or directly cooled from a heating temperature of 130Ā°C to room temperature.
- atactic polyolefin (e.g., atactic polypropylene) resin solution is cooled from a heating temperature to 70-80Ā°C and held at this temperature for 30-90 minutes, a better precipitation effect can be obtained.
- a polyethylene resin solution can be cooled from a heating temperature of 110Ā°C to 60-70Ā°C and held at this temperature for 30-90 minutes, and then cooled down to room temperature; or directly cooled from a heating temperature of 110Ā°C to room temperature.
- powder particles having a uniform particle size distribution can be obtained, which thus are particularly suitable for selective laser sintering applications.
- one or more adjuvants may optionally be added to the solid-liquid mixture.
- adjuvants are known in the processing of polyolefin resins and, particularly include powder release agents, antioxidants, antistatic agents, antibacterial agents and/or glass fiber reinforcements.
- the antioxidant may be selected from antioxidant 1010 and/or antioxidant 168, preferably a combination of both. More preferably, the antioxidant is used in an amount of 0.1-0.5 parts by weight, preferably 0.2-0.4 parts by weight, based on 100 parts by weight of the polyolefin resin.
- the inventors of the present invention have found in experiments that the addition of an antioxidant can not only prevent chain transfer of oxidation reaction, but also improve stability of the polyolefin resin such as polypropylene exposed to light, slow down oxidation of the polyolefin resin and increase heat-resistant stability and processing stability of the obtained polypropylene resin powder, thereby achieving the purpose of prolonging the service life.
- the powder release agent may be a metallic soap, i.e., an alkali or alkaline earth metal based on alkane monocarboxylic or dimer acids, preferably at least one selected from the group consisting of sodium stearate, potassium stearate, zinc stearate, calcium stearate and lead stearate.
- the powder release agent may also be a nano-oxide and/or a nano-metal salt, preferably at least one selected from the group consisting of silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, calcium carbonate and barium sulfate nanoparticles.
- the powder release agent is used in an amount of 0.01-10 parts by weight, preferably 0.1-5 parts by weight, and preferably 0.5-1 parts by weight, based on 100 parts by weight of the polyolefin resin.
- the powder release agent can be used to prevent adhesion among the polyolefin resin powder particles, thereby conducive to the processability thereof. On the other hand, it is also possible to prevent adhesion of antioxidants and make them more uniformly dispersed in the polyolefin resin to exert its antioxidant function. Further, the powder release agent can also act synergistically with antioxidants, and thus in particular, polyolefin resin powder with good dispersibility and flowability, which is suitable for selective laser sintering, can be obtained.
- the antistatic agent is at least one selected from the group consisting of carbon black, graphite, graphene, carbon nanotubes, and conductive metal powders/fibers and metal oxides, and is preferably at least one selected from the group consisting of acetylene black, superconductive carbon black, special conductive carbon black, natural graphite, expandable graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, gold, silver, copper, iron, aluminum, nickel or stainless steel component-containing metal powder/fibers, alloy powder/fibers, composite powder/fibers, titanium oxide, zinc oxide, tin oxide, indium oxide and cadmium oxide.
- the antistatic agent may be used in an amount of 0.05-15 parts by weight, preferably 0.1-10 parts by weight, and more preferably 0.25-5 parts by weight, based on 100 parts by weight of the polyolefin resin.
- the antistatic agent can be used to impart excellent antistatic performance to selective laser sintered polyolefin products, and in the meantime reduce the electrostatic interaction among the polyolefin resin powder particles and between the polyolefin resin powder particles and the device, thereby improving the processability thereof. Furthermore, the powdery antistatic agent may also serve as a barrier to improve the dispersibility and flowability among the polyolefin resin powder particles.
- the antibacterial agent is at least one selected from the group consisting of inorganic antibacterial agents such as supported types, nanometals and metal oxides and/or organic antibacterial agents such as organic guanidines, quaternary ammonium salts, phenol ethers, pyridines, imidazoles, isothiazolinones, and organometals, preferably at least one selected from the group consisting of zeolites, zirconium phosphate, calcium phosphate, hydroxyapatite, supported antimicrobial agents such as glass or activated carbon-supported silver ions, zinc ions or copper ions, nanogold or nanosilver, zinc oxide or titanium dioxide and polyhexamethylene guanidine hydrochloride or polyhexamethylene guanidine phosphate.
- inorganic antibacterial agents such as supported types, nanometals and metal oxides and/or organic antibacterial agents such as organic guanidines, quaternary ammonium salts, phenol ethers, pyridines, imidazo
- the antibacterial agent may be used in an amount of 0.05-1.5 parts by weight, preferably 0.05-1.0 parts by weight, more preferably 0.1-0.5 parts by weight, based on 100 parts by weight of the polyolefin resin.
- the antibacterial agent can be used to impart excellent antibacterial properties to selective laser sintered polyolefin products, and improve the hygienic safety of polyolefin products.
- the antibacterial agent when it is an inorganic powder, it can serve as an auxiliary barrier for the polyolefin resin powder to improve dispersibility and flowability.
- the glass fiber reinforcement is a glass fiber having a diameter of 5-20 ā m and a length of 100-500 ā m. It is preferably an alkali-free ultra-short glass fiber having a diameter of 5-15 ā m and a length of 100-250 ā m.
- the glass fiber reinforcement may be used in an amount of 5-60 parts by weight, preferably 5-50 parts by weight, and more preferably 10-50 parts by weight, based on 100 parts by weight of the polyolefin resin.
- the glass fiber added can effectively improve the physical and mechanical properties of polyolefin products. Meanwhile, due to a greater thermal shrinkage of polyolefin, the glass fiber added also contributes to the dimensional stability of polyolefin products.
- a second aspect of the present invention relates to polyolefin resin powders obtained according to the method of the present invention, the powder particles being spherical and/or spheroidal and having smooth surface, good dispersion and flowability, a uniform particle size distribution and suitable bulk density.
- the polyolefin resin powder provided according to the present invention is particularly suitable for selective laser sintering technology with a high success rate of sintering, and the obtained sintered product is featured with a small dimensional deviation from a predetermined product, less cross-sectional holes, a well-proportioned shape, and good mechanical properties.
- a third aspect of the present invention is to provide a selective laser sintering method, in which a polyolefin resin powder prepared by the method described above is used as a powdery raw material for sintering.
- a polyolefin molded product having a regular shape, a well-proportioned and smooth surface, and good mechanical properties can be prepared.
- a fourth aspect of the present invention relates to use of the polyolefin resin powders obtained according to the method of the present invention in a method of manufacturing a three-dimensional object, in particular a method in which a three-dimensional object is manufactured using selective laser sintering.
- the particle size and particle size distribution of the obtained polyolefin resin powders were characterized using a laser particle size analyzer (Mastersizer 2000, Malvern, UK).
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 130Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 90Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min.
- the resulting solid-liquid mixture were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 140Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 85Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 85Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min, and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min.
- the resulting solid-liquid mixture were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min.
- the resulting solid-liquid mixture were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min.
- the resulting solid-liquid mixture were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- atactic polypropylene resin isotacticity 93.9%, melt index (210Ā°C, 2.16 kg) 35 g/10 min, solubility parameter 16.7 MPa 1/2
- n-hexane solubility parameter 14.9 MPa 1/2
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min.
- the resulting solid-liquid mixture were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- atactic polypropylene resin isotacticity 94.1%, melt index (210Ā°C, 2.16 kg) 55 g/10 min, solubility parameter 16.7 MPa 1/2
- n-hexane solubility parameter 14.9 MPa 1/2
- a high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 130Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 75Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- atactic polypropylene resin isotacticity 92.6%, melt index (210Ā°C, 2.16 kg) 70 g/10 min, solubility parameter 16.7 MPa 1/2
- n-hexane solubility parameter 14.9 MPa 1/2
- a high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min.
- atactic polypropylene resin isotacticity 93.2%, melt index (210Ā°C, 2.16 kg) 60 g/10 min, solubility parameter 16.7 MPa 1/2
- n-hexane solubility parameter 14.9 MPa 1/2
- a high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 75Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min, and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- atactic polypropylene resin isotacticity 94%, melt index (210Ā°C, 2.16 kg) 65 g/10 min, solubility parameter 16.7 MPa 1/2
- n-hexane solubility parameter 14.9 MPa 1/2
- a high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 30Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 30 minutes.
- atactic polypropylene resin isotacticity 93.5%, melt index (210Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa 1/2
- n-heptane solubility parameter 15.2 MPa 1/2
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min.
- the resulting solid-liquid mixture were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- atactic polypropylene resin isotacticity 93.5%, melt index (210Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa 1/2
- n-pentane solubility parameter 14.4 MPa 1/2
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min.
- the resulting solid-liquid mixture were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- atactic polypropylene resin isotacticity 93.5%, melt index (210Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa 1/2
- n-octane solubility parameter 15.0 MPa 1/2
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min.
- the resulting solid-liquid mixture were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 130Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 90Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min.
- atactic polypropylene resin isotacticity 93.9%, melt index (210Ā°C, 2.16 kg) 35 g/10 min, solubility parameter 16.7 MPa 1/2
- n-hexane solubility parameter 14.9 MPa 1/2
- a high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min.
- a high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 65Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 65Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 55Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- a high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 90Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 55Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min, and held at this temperature for 60 minutes.
- the resulting solid-liquid mixture were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering.
- the particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- Example 1 35 ā 120 53 86 105 0.45
- Example 2 40 ā 130 55 94 118 0.41
- Example 3 30 ā 107 47 65 88 0.49
- Example 4 35 ā 130 52 78 108 0.45
- Example 5 30 ā 110 45 71 98 0.52
- Example 6 43 ā 137 55 85 113 0.42
- Example 7 45 ā 132 55 90 108 0.46
- Example 8 45 ā 130 52 81 104 0.44
- Example 9 35 ā 125 52 84 102 0.48
- Example 10 40 ā 120 58 81 97 0.45
- Example 11 25 ā 130 41 61 107 0.55
- Example 12 40 ā 135 55 86 109 0.44
- Example 13 30 ā 150 48 103 138 0.38
- Example 14 45 ā 120 58 80 95 0.42
- Example 15 42 ā 130 58 80 115 0.42
- Example 16 45 ā 127 64 85
- Example 1 was repeated except that nucleating agent calcium oxide was not used. Since there was no nucleating agent in this example, molten polypropylene had less nucleating points during crystallization and thus spherulite size was larger.
- Example 1 was repeated except that no antioxidant was used. Since there was no antioxidant in this example, the obtained polypropylene powder tended to be degraded and yellowing upon heating when used for laser sintering. Although the obtained polypropylene resin powder could satisfy the basic requirements of laser sintering process, the mechanical properties of the finished printed product were inadequate compared with Example 1.
- Example 1 was repeated except that no release agent was used. Since there was no release agent in this example, the obtained polypropylene powder tended to agglomerate in a small quantity, and had a slightly poorer flowability compared with Example 1. Although the obtained polypropylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product had a slightly worse surface smoothness.
- Example 20 was repeated except that no antioxidant was used. Since there was no antioxidant in this embodiment, the obtained polyethylene powder tended to be cross-linked upon heating when used for laser sintering compared with Example 20. Although the obtained polyethylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product was prone to shrink.
- Example 20 was repeated except that no release agent was used. Since there was no release agent in this example, the obtained polyethylene powder tended to agglomerate in a small quantity, and had a slightly poorer flowability compared with Example 20. Although the obtained polyethylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product had a slightly worse surface smoothness.
- Example 20 was repeated except that the release agent and the antioxidant were not used. Since there were neither release agent nor antioxidant in this example, the obtained polyethylene powder tended to be cross-linked upon heating when used for laser sintering, and tended to agglomerate in a small quantity, and had a slightly poorer flowability compared with Example 20. Although the obtained polyethylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product was prone to shrink and had a slightly worse surface smoothness.
- xylene solvent solubility parameter 18.2 MPa 1/2
- toluene solvent solubility parameter 18.4 MPa 1/2
- the polyolefin resin powder obtained according to the method of the present invention has good oxidation resistance, good powder flowability, moderate size, suitable bulk density, well-proportioned particle shape and uniform particle size distribution, which is suitable for selective laser sintering to prepare various molded products.
- the selective laser sintering method provided by the present invention polyolefin molded products having regular shape, smooth surface and good mechanical properties can be prepared.
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Abstract
Description
- The present invention relates to the technical field of polymer processing, in particular to a method for preparing a polyolefin resin powder and a polyolefin resin powder obtained thereby and its use for selective laser sintering.
- Selective Laser Sintering (SLS) technology is a rapid molding technology. It is currently most widely applicable and is the most promising technology in additive manufacturing technology showing in recent years a rapid development trend. The SLS technology is a method in which a computer first scans a three-dimensional solid article, and then high-strength laser light is used to irradiate material powders pre-spreading on a workbench or a component, and selectively melt-sinter it layer-by-layer, thereby realizing a layer-by-layer molding technology. The SLS technology has a high degree of design flexibility, is capable of producing accurate models and prototypes, and is capable of molding components that have reliable structure and can be used directly. Moreover, it shortens the production cycle and simplifies the process, so that it is particularly suitable for the development of new products. Theoretically, the types of molding materials that can be used for the SLS technology are relatively extensive, such as polymers, paraffins, metals, ceramics, and their composites. However, the performances and properties of molding materials are one of the essential factors to successful sintering of the SLS technology, because they directly affect the molding speed, precision, physical and chemical properties and overall performance of molded parts. Currently, the polymer powdery raw materials that can be directly applied to the SLS technology for successfully manufacturing molded products with small dimensional deviations, good surface regularity, and low porosity are rarely seen in the market. Therefore, it is urgent to develop and improve the polymer types applicable to the SLS technology and their corresponding solid powdery raw materials.
- In the prior art, a pulverization method such as a cryogenic pulverization method is generally used to prepare powdery raw materials suitable for the SLS. For example, polypropylene powders obtained by cryogenic pulverization method is disclosed in
CN104031319A . However, on one hand, this method requires a specific equipment. On the other hand, the surface of the prepared powdery raw material particle is rough, the particle size is not uniform enough, and the shape is irregular, which is not conducive to the formation of sintered molded body and affects the performance of the molded body. - In addition, a precipitation method may be used to prepare polymer powdery raw materials, such as polyamide powders. In this method, the polyamide is usually dissolved in a suitable solvent, uniformly dispersed in the solvent by stirring, and then the powders are precipitated upon cooling.
- For example,
CN103374223A discloses a precipitation polymer powder based on an AABB-type polyamide, which is obtained by reprecipitating a polyamide formed by polycondensation of a diamine and a dicarboxylic acid. In the method described in this patent, alcoholic solvents are used during reprecipitation. - A first aspect of the present invention is to provide a polyolefin resin powder and a preparation method thereof and its use for selective laser sintering. The polyolefin resin powder provided according to the present invention has good oxidation resistance, good powder flowability, moderate size, suitable bulk density, well-proportioned particle shape and uniform particle size distribution, which is particularly suitable for selective laser sintering to prepare various molded articles.
- The method for preparing a polyolefin resin powder according to the present invention includes the following steps:
- a) heat dissolving a polyolefin resin in an organic solvent having a solubility parameter less than or equal to the solubility parameter of the polyolefin resin to obtain a polyolefin resin solution;
- b) cooling the polyolefin resin solution to precipitate a solid, thereby obtaining a solid-liquid mixture;
- c) optionally adding an adjuvant to the solid-liquid mixture and mixing;
- d) conducting solid-liquid separation and drying to obtain a polyolefin resin powder suitable for selective laser sintering;
- A second aspect of the present invention lies in a polyolefin resin powder obtained according to the method of the present invention.
- A third aspect of the present invention lies in a selective laser sintering method. A fourth aspect of the present invention lies in use of a polyolefin resin powder obtained according to the method of the present invention in a method of producing a three-dimensional object.
- In the preparation method of the polyolefin resin powder according to the present invention, there is no particular limitation on a suitable polyolefin as long as it can be made in the form of a powder material.
- Polyolefins suitable for use in the method of the present invention may be selected from polymers which are obtained by polymerizing or copolymerizing linear, branched or cyclic olefins, e.g. C2-C10 olefins, preferably Ī±-olefins, or mixtures of these polymers. Suitable olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and the like.
- In a preferred embodiment, the polyolefin is selected from polypropylene (PP) and polyethylene (PE) or mixtures thereof. More preferably, the polyolefin is one of polypropylene or polyethylene.
- In another preferred embodiment, the polypropylene is at least one selected from the group consisting of homopolypropylene resin and atactic polypropylene resin. Preferably, the homopolypropylene resin has an isotacticity of ā„ 95%, for example 95-98%; and the atactic polypropylene resin has an isotacticity of < 95%, for example 91-94.5%.
- In a preferred embodiment of the present invention, the homopolypropylene resin and the atactic polypropylene resin have a melt index, measured at 210Ā°C and a load of 2.16 kg, of 20-100 g/10 min, preferably 30-80 g/10 min. In another preferred embodiment of the present invention, the polyethylene resin has a density of ā„ 0.900 g/cm3, preferably 0.910-0.990 g/cm3; a melt index, measured at 190Ā°C and a load of 2.16 kg, of 20-100 g/10 min, preferably 30-80 g/10 min. Within these ranges, the polyolefin resin exhibits good flowability, which is advantageous to the laser sintering process.
- Although organic solvent precipitation technology has been used for separation and purification of biochemical substances, especially protein, or for precipitation to prepare crystals, there are currently few reports on the preparation of resin powdery material using organic solvent precipitation method, particularly polyolefin resin powders, which can be used for selective laser sintering. In the method according to the present invention, it is important to select out the organic solvent for dissolving the polyolefin resin which should be a poor solvent for the aforementioned polyolefin resin under normal temperature and normal pressure. Therefore, the organic solvent is selected to have a solubility parameter less than or equal to the solubility parameter of the polyolefin resin, and the difference is within 0-20%, preferably within 0-15%, for example, within 0-12% of the solubility parameter of the polyolefin resin.
- In addition, in another advantageous embodiment, the solvent is further selected to be a low boiling solvent. In the context of the present invention, the term "low boiling (solvent)" means that the solvent has a boiling point of no more than 160Ā°C, such as no more than 150Ā°C or 130Ā°C, at normal pressure. Preferably, in step a), the organic solvent is used in an amount of 600-1200 parts by weight, preferably 800-1000 parts by weight, based on 100 parts by weight of the polyolefin resin. When the organic solvent is used in an amount within this range, a polyolefin resin powder having good morphology and dispersibility can be obtained.
- In an advantageous embodiment, the organic solvent is selected from C5-C12 alkanes, preferably C5-C9 alkanes, more preferably at least one selected from the group consisting of n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, n-octane, and n-nonane.
- In a more preferred embodiment, the organic solvent is selected from C6-C8 alkanes such as n-hexane, n-heptane and/or n-octane.
- The inventors of the present invention have further found through extensive experiments that when using the above organic solvents, particularly n-hexane and/or n-heptane, to dissolve the polyolefin resin and cooling to precipitate, the polyolefin resin can precipitate in a spherical and/or spheroidal shape, with a particle size of 25-150 Āµm. The obtained polyolefin resin powder has smooth surface, good dispersibility and small size distribution, and is particularly suitable for selective laser sintering technology.
- In step a) of the method according to the present invention, the polyolefin resin is advantageously heated to a temperature of 60-200Ā°C, e.g., 70-190Ā°C or 80-160Ā°C. In a specific embodiment, polypropylene resin is heated to 90-180Ā°C, preferably 100-150Ā°C, more preferably 110-140Ā°C. In another specific embodiment, polyethylene resin is heated to 70-150Ā°C, preferably 80-130Ā°C, more preferably 90-110Ā°C.
- In a preferred embodiment, the polyolefin resin solution may be held at said heating temperature for 30-90 minutes for sufficient dissolution. In addition, it is also preferable to perform the heating under an inert gas which is preferably nitrogen and which pressure may be 0.1-0.5 MPa, preferably 0.2-0.3 MPa.
- In the method according to the present invention, the dissolution of step a) and the reprecipitation of step b) are advantageously carried out under pressure. The pressure can be established by vapor pressure of a solvent in a closed system.
- In addition, a nucleating agent may optionally be added in step a). Said nucleating agent is at least one selected from the group consisting of silica, calcium oxide, calcium carbonate, barium sulfate, hydrotalcite, talc, carbon black, kaolin and mica. The nucleating agent may be used in an amount of 0.01-2 parts by weight, preferably 0.05-1 parts by weight, and more preferably 0.1-0.5 parts by weight, based on 100 parts by weight of the polyolefin resin. The inventors of the present invention have found in experiments that, when these nucleating agents are added, the crystallization rate of the polyolefin resin can be increased, and the surface smoothness, heat resistance, and mechanical properties of the obtained polyolefin powder can be improved. Preferably, a nucleating agent is used in the case when a polypropylene resin powder is used as the polyolefin resin.
- In step b), preferably, the average cooling rate is 0.1Ā°C/min to 1Ā°C/min. In addition, the polyolefin resin solution is preferably cooled down to a target temperature and held at the target temperature for 30-90 minutes, wherein the target temperature is preferably 10-30Ā°C, for example, room temperature (i.e., about 25Ā°C).
- The cooling of the polyolefin resin solution can be performed at a uniform rate in one step, or it can be performed in a stepwise manner. In a preferred embodiment of step b), the polyolefin resin solution is cooled to a target temperature via one or more intermediate temperatures and held at said intermediate temperatures for 30-90 minutes, said intermediate temperatures being in the range of 40-100Ā°C, for example, 50-90Ā°C. For example, for polypropylene, the intermediate temperature is preferably 60-100Ā°C, more preferably 70-90Ā°C; for polyethylene, the intermediate temperature is preferably 40-80Ā°C, more preferably 50-70Ā°C. This will bring out a better precipitation effect. When two or more intermediate temperatures are used, it is advantageous to make the difference between two adjacent intermediate temperatures above 10Ā°C.
- It is easily understood that the intermediate temperature refers to the temperature between the heating temperature of step a) and the target temperature of step b). For example, in a specific embodiment, a homopolyolefin (e.g., homopolypropylene) resin solution can be cooled from a heating temperature of 130Ā°C to 90Ā°C and held at 90Ā°C for 60 minutes, and then cooled down to room temperature; or directly cooled from a heating temperature of 130Ā°C to room temperature. In another preferred embodiment, if atactic polyolefin (e.g., atactic polypropylene) resin solution is cooled from a heating temperature to 70-80Ā°C and held at this temperature for 30-90 minutes, a better precipitation effect can be obtained. In another specific embodiment, a polyethylene resin solution can be cooled from a heating temperature of 110Ā°C to 60-70Ā°C and held at this temperature for 30-90 minutes, and then cooled down to room temperature; or directly cooled from a heating temperature of 110Ā°C to room temperature.
- With the heating and cooling manners of the present invention, powder particles having a uniform particle size distribution can be obtained, which thus are particularly suitable for selective laser sintering applications.
- In addition, in step c) of the method according to the present invention, one or more adjuvants may optionally be added to the solid-liquid mixture. These adjuvants are known in the processing of polyolefin resins and, particularly include powder release agents, antioxidants, antistatic agents, antibacterial agents and/or glass fiber reinforcements.
- The antioxidant may be selected from antioxidant 1010 and/or antioxidant 168, preferably a combination of both. More preferably, the antioxidant is used in an amount of 0.1-0.5 parts by weight, preferably 0.2-0.4 parts by weight, based on 100 parts by weight of the polyolefin resin.
- The inventors of the present invention have found in experiments that the addition of an antioxidant can not only prevent chain transfer of oxidation reaction, but also improve stability of the polyolefin resin such as polypropylene exposed to light, slow down oxidation of the polyolefin resin and increase heat-resistant stability and processing stability of the obtained polypropylene resin powder, thereby achieving the purpose of prolonging the service life.
- The powder release agent may be a metallic soap, i.e., an alkali or alkaline earth metal based on alkane monocarboxylic or dimer acids, preferably at least one selected from the group consisting of sodium stearate, potassium stearate, zinc stearate, calcium stearate and lead stearate. In addition, the powder release agent may also be a nano-oxide and/or a nano-metal salt, preferably at least one selected from the group consisting of silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, calcium carbonate and barium sulfate nanoparticles.
- In the present invention, the powder release agent is used in an amount of 0.01-10 parts by weight, preferably 0.1-5 parts by weight, and preferably 0.5-1 parts by weight, based on 100 parts by weight of the polyolefin resin.
- The powder release agent can be used to prevent adhesion among the polyolefin resin powder particles, thereby conducive to the processability thereof. On the other hand, it is also possible to prevent adhesion of antioxidants and make them more uniformly dispersed in the polyolefin resin to exert its antioxidant function. Further, the powder release agent can also act synergistically with antioxidants, and thus in particular, polyolefin resin powder with good dispersibility and flowability, which is suitable for selective laser sintering, can be obtained.
- The antistatic agent is at least one selected from the group consisting of carbon black, graphite, graphene, carbon nanotubes, and conductive metal powders/fibers and metal oxides, and is preferably at least one selected from the group consisting of acetylene black, superconductive carbon black, special conductive carbon black, natural graphite, expandable graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, gold, silver, copper, iron, aluminum, nickel or stainless steel component-containing metal powder/fibers, alloy powder/fibers, composite powder/fibers, titanium oxide, zinc oxide, tin oxide, indium oxide and cadmium oxide.
- In the present invention, the antistatic agent may be used in an amount of 0.05-15 parts by weight, preferably 0.1-10 parts by weight, and more preferably 0.25-5 parts by weight, based on 100 parts by weight of the polyolefin resin.
- The antistatic agent can be used to impart excellent antistatic performance to selective laser sintered polyolefin products, and in the meantime reduce the electrostatic interaction among the polyolefin resin powder particles and between the polyolefin resin powder particles and the device, thereby improving the processability thereof. Furthermore, the powdery antistatic agent may also serve as a barrier to improve the dispersibility and flowability among the polyolefin resin powder particles.
- The antibacterial agent is at least one selected from the group consisting of inorganic antibacterial agents such as supported types, nanometals and metal oxides and/or organic antibacterial agents such as organic guanidines, quaternary ammonium salts, phenol ethers, pyridines, imidazoles, isothiazolinones, and organometals, preferably at least one selected from the group consisting of zeolites, zirconium phosphate, calcium phosphate, hydroxyapatite, supported antimicrobial agents such as glass or activated carbon-supported silver ions, zinc ions or copper ions, nanogold or nanosilver, zinc oxide or titanium dioxide and polyhexamethylene guanidine hydrochloride or polyhexamethylene guanidine phosphate.
- In the present invention, the antibacterial agent may be used in an amount of 0.05-1.5 parts by weight, preferably 0.05-1.0 parts by weight, more preferably 0.1-0.5 parts by weight, based on 100 parts by weight of the polyolefin resin. The antibacterial agent can be used to impart excellent antibacterial properties to selective laser sintered polyolefin products, and improve the hygienic safety of polyolefin products. Furthermore, when the antibacterial agent is an inorganic powder, it can serve as an auxiliary barrier for the polyolefin resin powder to improve dispersibility and flowability.
- The glass fiber reinforcement is a glass fiber having a diameter of 5-20 Āµm and a length of 100-500 Āµm. It is preferably an alkali-free ultra-short glass fiber having a diameter of 5-15 Āµm and a length of 100-250 Āµm. In the present invention, the glass fiber reinforcement may be used in an amount of 5-60 parts by weight, preferably 5-50 parts by weight, and more preferably 10-50 parts by weight, based on 100 parts by weight of the polyolefin resin.
- The glass fiber added can effectively improve the physical and mechanical properties of polyolefin products. Meanwhile, due to a greater thermal shrinkage of polyolefin, the glass fiber added also contributes to the dimensional stability of polyolefin products.
- A second aspect of the present invention relates to polyolefin resin powders obtained according to the method of the present invention, the powder particles being spherical and/or spheroidal and having smooth surface, good dispersion and flowability, a uniform particle size distribution and suitable bulk density. Preferably, the polyolefin resin powder particles have a particle size of 25-150 Āµm, and a particle size distribution D10 = 41-69 Āµm, D50 = 61-103 Āµm, and D90 = 85-138 Āµm. The polyolefin resin powder provided according to the present invention is particularly suitable for selective laser sintering technology with a high success rate of sintering, and the obtained sintered product is featured with a small dimensional deviation from a predetermined product, less cross-sectional holes, a well-proportioned shape, and good mechanical properties.
- In addition, a third aspect of the present invention is to provide a selective laser sintering method, in which a polyolefin resin powder prepared by the method described above is used as a powdery raw material for sintering. According to the selective laser sintering method provided by the present invention, a polyolefin molded product having a regular shape, a well-proportioned and smooth surface, and good mechanical properties can be prepared.
- Finally, a fourth aspect of the present invention relates to use of the polyolefin resin powders obtained according to the method of the present invention in a method of manufacturing a three-dimensional object, in particular a method in which a three-dimensional object is manufactured using selective laser sintering.
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Figure 1 is a scanning electron microscope (SEM) image of a polypropylene resin powder provided according to Example 1 of the present invention. -
Figure 2 is a scanning electron microscope (SEM) image of a polyethylene resin powder provided according to Example 17 of the present invention. -
Figure 3 is a scanning electron microscope image of commercially available polyamide 12 powder for selective laser sintering which is prepared by reprecipitation, for comparison with the present invention (Figures 1 and 2 ). - The present invention will be further illustrated by the following specific examples, but it should be understood that the scope of the present invention is not limited thereto.
- In the following examples, the particle size and particle size distribution of the obtained polyolefin resin powders were characterized using a laser particle size analyzer (Mastersizer 2000, Malvern, UK).
- 100 parts by weight of homopolypropylene resin (isotacticity 95%, melt index (210Ā°C, 2.16 kg) 30 g/10 min, solubility parameter 16.7 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.2 parts by weight of calcium oxide was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 130Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 90Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 97%, melt index (210Ā°C, 2.16 kg) 50 g/10 min, solubility parameter 16.7 MPa1/2) and 800 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.4 parts by weight of calcium oxide was added and mixed. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 140Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 85Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 96%, melt index (210Ā°C, 2.16 kg) 50 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.8 parts by weight of calcium oxide was added and mixed. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min. In the resulting solid-liquid mixture, were added 0.1 parts by weight of antioxidant 1010 and 0.1 parts by weight of antioxidant 168 as well as 0.75 parts by weight of nano-silica, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 96%, melt index (210Ā°C, 2.16 kg) 80 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.3 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 85Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min, and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 96%, melt index (210Ā°C, 2.16 kg) 60 g/10 min, solubility parameter 16.7 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.5 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 140Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 30Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 30 minutes. In the resulting solid-liquid mixture, were added 0.2 parts by weight of antioxidant 1010 and 0.2 parts by weight of antioxidant 168 as well as 0.6 parts by weight of nano-calcium carbonate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 95%, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-heptane (solubility parameter 15.2 MPa1/2) were placed in an autoclave, and 0.9 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 95%, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of cyclohexane (solubility parameter 16.6 MPa1/2) were placed in an autoclave, and 0.2 parts by weight of silica was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 95%, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of 2,2,3-trimethylbutane (solubility parameter 15.7 MPa1/2) were placed in an autoclave, and 0.3 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 93.9%, melt index (210Ā°C, 2.16 kg) 35 g/10 min, solubility parameter 16.7 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.2 parts by weight of silica was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 94.1%, melt index (210Ā°C, 2.16 kg) 55 g/10 min, solubility parameter 16.7 MPa1/2) and 800 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.4 parts by weight of silica was added and mixed. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 130Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 75Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 92.6%, melt index (210Ā°C, 2.16 kg) 70 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.8 parts by weight of silica was added and mixed. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min. In the resulting solid-liquid mixture, were added 0.1 parts by weight of antioxidant 1010 and 0.1 parts by weight of antioxidant 168 as well as 0.75 parts by weight of nano-silica, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 93.2%, melt index (210Ā°C, 2.16 kg) 60 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.3 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 75Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min, and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 94%, melt index (210Ā°C, 2.16 kg) 65 g/10 min, solubility parameter 16.7 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.5 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 30Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 30 minutes. In the resulting solid-liquid mixture, were added 0.2 parts by weight of antioxidant 1010 and 0.2 parts by weight of antioxidant 168 as well as 0.6 parts by weight of nano-calcium carbonate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 93.5%, melt index (210Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-heptane (solubility parameter 15.2 MPa1/2) were placed in an autoclave, and 0.9 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 93.5%, melt index (210Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-pentane (solubility parameter 14.4 MPa1/2) were placed in an autoclave, and 0.2 parts by weight of silica was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 93.5%, melt index (210Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-octane (solubility parameter 15.0 MPa1/2) were placed in an autoclave, and 0.3 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 95%, melt index (210Ā°C, 2.16 kg) 35 g/10 min, solubility parameter 16.7 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.2 parts by weight of calcium oxide was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 130Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 90Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate and 0.5 parts by weight of single walled carbon nanotubes, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of homopolypropylene resin (isotacticity 96%, melt index (210Ā°C, 2.16 kg) 45 g/10 min, solubility parameter 16.7 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.3 parts by weight of kaolin was added and mixed. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min. In the resulting solid-liquid mixture, were added 0.1 parts by weight of antioxidant 1010 and 0.1 parts by weight of antioxidant 168, 0.75 parts by weight of nano-silica and 0.5 parts by weight of silver-zirconium phosphate antibacterial agent, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of atactic polypropylene resin (isotacticity 93.9%, melt index (210Ā°C, 2.16 kg) 35 g/10 min, solubility parameter 16.7 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave, and 0.2 parts by weight of silica was added and mixed. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 80Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168, 0.5 parts by weight of calcium stearate and 25 parts by weight of ultra-short glass fibers with a diameter of 10 Āµm and a length of 250 Āµm, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain an atactic polypropylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polypropylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.950 g/cm3, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.960 g/cm3, melt index (190Ā°C, 2.16 kg) 60 g/10 min, solubility parameter 17.0 MPa1/2) and 800 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 120Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 65Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.970 g/cm3, melt index (190Ā°C, 2.16 kg) 50 g/10 min, solubility parameter 17.0 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min. In the resulting solid-liquid mixture, were added 0.1 parts by weight of antioxidant 1010 and 0.1 parts by weight of antioxidant 168 as well as 0.75 parts by weight of nano-silica and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.954 g/cm3, melt index (190Ā°C, 2.16 kg) 70 g/10 min, solubility parameter 17.0 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 65Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.948 g/cm3, melt index (190Ā°C, 2.16 kg) 65 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 30Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 30 minutes. In the resulting solid-liquid mixture, were added 0.2 parts by weight of antioxidant 1010 and 0.2 parts by weight of antioxidant 168 as well as 0.6 parts by weight of nano-calcium carbonate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.962 g/cm3, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 17.0 MPa1/2) and 1200 parts by weight of n-heptane (solubility parameter 15.2 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 60Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.950 g/cm3, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of cyclohexane (solubility parameter 16.6 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.950 g/cm3, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of 2,2,3-trimethylbutane (solubility parameter 15.7 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.930 g/cm3, melt index (190Ā°C, 2.16 kg) 30 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 60Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.927 g/cm3, melt index (190Ā°C, 2.16 kg) 70 g/10 min, solubility parameter 17.0 MPa1/2) and 800 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 55Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to 20Ā°C at a rate of 1.0Ā°C/min, and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 1 part by weight of zinc stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.920 g/cm3, melt index (190Ā°C, 2.16 kg) 50 g/10 min, solubility parameter 17.0 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 90Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min. In the resulting solid-liquid mixture, were added 0.1 parts by weight of antioxidant 1010 and 0.1 parts by weight of antioxidant 168 as well as 0.75 parts by weight of nano-silica, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.915 g/cm3, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 17.0 MPa1/2) and 1200 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.1 MPa; then the autoclave was heated up to 90Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 55Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.1Ā°C/min, and held at this temperature for 60 minutes. In the resulting solid-liquid mixture, were added 0.3 parts by weight of antioxidant 1010 and 0.3 parts by weight of antioxidant 168 as well as 0.9 parts by weight of nano-zinc oxide, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.935 g/cm3, melt index (190Ā°C, 2.16 kg) 60 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 90Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 30Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 30 minutes. In the resulting solid-liquid mixture, were added 0.2 parts by weight of antioxidant 1010 and 0.2 parts by weight of antioxidant 168 as well as 0.6 parts by weight of nano-calcium carbonate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.924 g/cm3, melt index (190Ā°C, 2.16 kg) 45 g/10 min, solubility parameter 17.0 MPa1/2) and 1200 parts by weight of n-heptane (solubility parameter 15.2 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 90Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 50Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168 as well as 0.8 parts by weight of sodium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.930 g/cm3, melt index (190Ā°C, 2.16 kg) 30 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-pentane (solubility parameter 14.4 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 60Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.930 g/cm3, melt index (190Ā°C, 2.16 kg) 30 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-octane (solubility parameter 15.4 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 60Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168 as well as 0.5 parts by weight of calcium stearate, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.950 g/cm3, melt index (190Ā°C, 2.16 kg) 35 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 110Ā°C, and held at this temperature for 60 minutes; thereafter, the autoclave was cooled down to 70Ā°C at a rate of 1.0Ā°C/min with cooling water, and held at this temperature for 60 minutes; further, the autoclave was cooled down to room temperature at a rate of 1.0Ā°C/min. In the resulting solid-liquid mixture, were added 0.25 parts by weight of antioxidant 1010 and 0.25 parts by weight of antioxidant 168, 0.5 parts by weight of calcium stearate, 2.5 parts by weight of conductive carbon black as well as 0.1 parts by weight of carbon nanotubes, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.948 g/cm3, melt index (190Ā°C, 2.16 kg) 60 g/10 min, solubility parameter 17.0 MPa1/2) and 1000 parts by weight of n-hexane (solubility parameter 14.9 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.3 MPa; then the autoclave was heated up to 100Ā°C, and held at this temperature for 30 minutes; thereafter, the autoclave was cooled down to 30Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 30 minutes. In the resulting solid-liquid mixture, were added 0.2 parts by weight of antioxidant 1010 and 0.2 parts by weight of antioxidant 168, 0.6 parts by weight of nano-calcium carbonate as well as 0.05 parts by weight of zinc pyrithione, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
- 100 parts by weight of polyethylene resin (density 0.924 g/cm3, melt index (190Ā°C, 2.16 kg) 40 g/10 min, solubility parameter 17.0 MPa1/2) and 1200 parts by weight of n-heptane (solubility parameter 15.2 MPa1/2) were placed in an autoclave. A high-purity nitrogen gas was charged to 0.2 MPa; then the autoclave was heated up to 90Ā°C, and held at this temperature for 90 minutes; thereafter, the autoclave was cooled down to 50Ā°C at a rate of 0.5Ā°C/min with cooling water, and held at this temperature for 90 minutes; further, the autoclave was cooled down to room temperature at a rate of 0.2Ā°C/min. In the resulting solid-liquid mixture, were added 0.15 parts by weight of antioxidant 1010 and 0.15 parts by weight of antioxidant 168, 0.8 parts by weight of sodium stearate as well as 50 parts by weight of ultra-short glass fibers with a diameter of 5 Āµm and a length of 150 Āµm, and thereafter the material was subjected to centrifugal separation and vacuum drying to obtain a polyethylene resin powder suitable for selective laser sintering. The particle size and particle size distribution of the obtained polyethylene resin powder were listed in Table 1.
Table 1 Example Particle size (Āµm) D10 (Āµm) D50 (Āµm) D90 (Āµm) Bulk density (g/cm3) Example 1 35ā¼120 53 86 105 0.45 Example 2 40ā¼130 55 94 118 0.41 Example 3 30ā¼107 47 65 88 0.49 Example 4 35ā¼130 52 78 108 0.45 Example 5 30ā¼110 45 71 98 0.52 Example 6 43ā¼137 55 85 113 0.42 Example 7 45ā¼132 55 90 108 0.46 Example 8 45ā¼130 52 81 104 0.44 Example 9 35ā¼125 52 84 102 0.48 Example 10 40ā¼120 58 81 97 0.45 Example 11 25ā¼130 41 61 107 0.55 Example 12 40ā¼135 55 86 109 0.44 Example 13 30ā¼150 48 103 138 0.38 Example 14 45ā¼120 58 80 95 0.42 Example 15 42ā¼130 58 80 115 0.42 Example 16 45ā¼127 64 85 115 0.44 Example 17 45ā¼135 49 84 122 0.43 Example 18 42ā¼125 56 82 105 0.44 Example 19 40ā¼130 50 84 108 0.42 Example 20 45ā¼135 59 90 112 0.44 Example 21 40ā¼130 55 94 115 0.45 Example 22 30ā¼127 48 75 101 0.57 Example 23 35ā¼130 50 89 110 0.50 Example 24 35ā¼120 49 71 95 0.52 Example 25 40ā¼130 56 85 106 0.47 Example 26 42ā¼130 58 80 115 0.44 Example 27 45ā¼127 64 85 115 0.45 Example 28 35ā¼115 45 71 92 0.56 Example 29 50ā¼130 61 91 115 0.40 Example 30 30ā¼100 46 66 85 0.54 Example 31 35ā¼120 52 79 100 0.50 Example 32 50ā¼150 69 97 120 0.37 Example 33 45ā¼130 67 96 114 0.43 Example 34 45ā¼132 55 90 108 0.43 Example 35 45ā¼130 52 81 104 0.46 Example 36 30ā¼110 46 74 90 0.52 Example 37 50ā¼130 65 88 115 0.48 Example 38 45ā¼120 58 85 110 0.41 - Example 1 was repeated except that nucleating agent calcium oxide was not used. Since there was no nucleating agent in this example, molten polypropylene had less nucleating points during crystallization and thus spherulite size was larger. The finally obtained polypropylene powder particles for laser sintering had a larger particle size, ranging from 70 to 150 Āµm, with D10 = 92 Āµm, D50 = 113 Āµm, and D90 = 132 Āµm. Although the obtained polypropylene resin powder could satisfy the basic requirements of laser sintering process, it had a greater fraction of particles with larger size than that of Example 1.
- Example 1 was repeated except that no antioxidant was used. Since there was no antioxidant in this example, the obtained polypropylene powder tended to be degraded and yellowing upon heating when used for laser sintering. Although the obtained polypropylene resin powder could satisfy the basic requirements of laser sintering process, the mechanical properties of the finished printed product were inadequate compared with Example 1.
- Example 1 was repeated except that no release agent was used. Since there was no release agent in this example, the obtained polypropylene powder tended to agglomerate in a small quantity, and had a slightly poorer flowability compared with Example 1. Although the obtained polypropylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product had a slightly worse surface smoothness.
- Example 20 was repeated except that no antioxidant was used. Since there was no antioxidant in this embodiment, the obtained polyethylene powder tended to be cross-linked upon heating when used for laser sintering compared with Example 20. Although the obtained polyethylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product was prone to shrink.
- Example 20 was repeated except that no release agent was used. Since there was no release agent in this example, the obtained polyethylene powder tended to agglomerate in a small quantity, and had a slightly poorer flowability compared with Example 20. Although the obtained polyethylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product had a slightly worse surface smoothness.
- Example 20 was repeated except that the release agent and the antioxidant were not used. Since there were neither release agent nor antioxidant in this example, the obtained polyethylene powder tended to be cross-linked upon heating when used for laser sintering, and tended to agglomerate in a small quantity, and had a slightly poorer flowability compared with Example 20. Although the obtained polyethylene resin powder could satisfy the basic requirements of laser sintering process, the finished printed product was prone to shrink and had a slightly worse surface smoothness.
- Example 1 was repeated except that xylene solvent (solubility parameter 18.2 MPa1/2) was used instead of n-hexane solvent. Since the xylene solvent used in this comparative example was a good solvent for polypropylene, the polypropylene, after dissolved, had a very slow crystallization rate upon cooling. In the same experimental time as that in Example 1, the particle size of the obtained polypropylene powder particles for laser sintering was too small and the particle size distribution was worse (the particle size ranging from 10 to 55 Āµm, D10 = 15 Āµm, D50 = 24 Āµm, D90 = 49 Āµm). The obtained polypropylene resin powder could not satisfactorily meet the requirements of laser sintering process.
- Example 1 was repeated except that toluene solvent (solubility parameter 18.4 MPa1/2) was used instead of n-hexane solvent. Since the toluene solvent used in this comparative example was a good solvent for polypropylene, the polypropylene, after dissolved, had a very slow crystallization rate upon cooling. In the same experimental time as that in Example 1, the particle size of the obtained polypropylene powder particles for laser sintering was too small and the particle size distribution was worse (the particle size ranging from 16 to 52 Āµm, D10 = 25 Āµm, D50 = 34 Āµm, D90 = 40 Āµm). The obtained polypropylene resin powder could not satisfactorily meet the requirements of laser sintering process.
- The above examples and comparative examples illustrate that the polyolefin resin powder obtained according to the method of the present invention has good oxidation resistance, good powder flowability, moderate size, suitable bulk density, well-proportioned particle shape and uniform particle size distribution, which is suitable for selective laser sintering to prepare various molded products. With the selective laser sintering method provided by the present invention, polyolefin molded products having regular shape, smooth surface and good mechanical properties can be prepared.
- Although the present invention has been described in detail, modifications within the spirit and scope of the present invention will be apparent to those skilled in the art. In addition, it should be understood that various aspects of the present invention described herein, various parts of different embodiments, and various features listed may be combined or totally or partially interchanged. In the respective embodiments described above, those embodiments that refer to another specific embodiment can be combined with other embodiments as appropriate, as will be understood by those skilled in the art. Moreover, those skilled in the art will understand that the foregoing description is by way of example only and is not intended to limit the present invention.
Claims (16)
- A method for preparing a polyolefin resin powder, containing the following steps:a) heat dissolving a polyolefin resin in an organic solvent having a solubility parameter less than or equal to the solubility parameter of the polyolefin resin to obtain a polyolefin resin solution;b) cooling the polyolefin resin solution to precipitate a solid, thereby obtaining a solid-liquid mixture;c) optionally adding an adjuvant to the solid-liquid mixture and mixing;d) conducting solid-liquid separation and drying to obtain a polyolefin resin powder suitable for selective laser sintering;wherein the difference between the solubility parameters of the organic solvent and of the polyolefin resin is within 0-20% of the solubility parameter of the polyolefin resin.
- The method according to claim 1, which is characterized in that, in step a), the polyolefin resin is at least one selected from the group consisting of polypropylene and polyethylene resins, preferably at least one selected from the group consisting of homopolypropylene resin and atactic polypropylene resin.
- The method according to claim 1 or 2, which is characterized in that the homopolypropylene resin and the atactic polypropylene resin have a melt index, measured at 210Ā°C and a load of 2.16 kg, of 20-100 g/10 min, preferably 30-80 g/10 min; the polyethylene resin has a melt index, measured at 190Ā°C and a load of 2.16 kg, of 20-100 g/10 min, preferably 30-80 g/10 min.
- The method according to any one of claims 1 to 3, which is characterized in that the organic solvent is used in an amount of 600-1200 parts by weight, preferably 800-1000 parts by weight, based on 100 parts by weight of the polyolefin resin.
- The method according to any one of claims 1 to 4, which is characterized in that the organic solvent is selected from C5-C12 alkanes, preferably C5-C9 alkanes, more preferably at least one selected from the group consisting of n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, n-octane, and n-nonane, and most preferably n-hexane, n-heptane and/or n-octane.
- The method according to any one of claims 1 to 5, which is characterized in that, in step a), the polyolefin resin is heated to a temperature of 60-200Ā°C, e.g., 70-190Ā°C or 80-160Ā°C; and preferably the polyolefin resin solution is held at the heating temperature for 30-90 minutes.
- The method according to any one of claims 1 to 6, which is characterized in that, in step b), the polyolefin resin solution is cooled down to a target temperature at an average cooling rate of 0.1Ā°C/min to 1Ā°C/min, and is held for 30-90 minutes at the target temperature which is 10-30Ā°C.
- The method according to any one of claims 1 to 7, which is characterized in that, in step b), the polyolefin resin solution is cooled to a target temperature via one or more intermediate temperatures and held for 30-90 minutes at said intermediate temperatures which are in the range of 40-100Ā°C or 50-90Ā°C.
- The method according to any one of claims 1 to 8, which is characterized in that a nucleating agent is added in step a), which is preferably at least one selected from the group consisting of silica, calcium oxide, calcium carbonate, barium sulfate, hydrotalcite, hydrotalcite, carbon black, kaolin and mica.
- The method according to claim 9, which is characterized in that the nucleating agent is used in an amount of 0.01-2 parts by weight, preferably 0.05-1 parts by weight, and more preferably 0.1-0.5 parts by weight, based on 100 parts by weight of the polyolefin resin.
- The method according to any one of claims 1 to 10, which is characterized in that the adjuvant in step c) is selected from antioxidants, powder release agents, antistatic agents, antibacterial agents and/or glass fiber reinforcements, preferably antioxidants and/or powder release agents.
- The method according to claim 11, which is characterized in that the antioxidant is selected from antioxidant 1010 and/or antioxidant 168 which is preferably used in an amount of 0.1-0.5 parts by weight, more preferably 0.2-0.4 parts by weight, based on 100 parts by weight of the polyolefin resin.
- The method according to claim 11, which is characterized in that the powder release agent is at least one selected from an alkali or alkaline earth metal based on alkane monocarboxylic or dimer acids, a nano-oxide and a nano-metal salt, preferably at least one selected from the group consisting of sodium stearate, potassium stearate, zinc stearate, calcium stearate, lead stearate, silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, calcium carbonate and barium sulfate; and the powder release agent is used in an amount of 0.01-10 parts by weight, preferably 0.1-5 parts by weight, and more preferably 0.5-1 parts by weight, based on 100 parts by weight of the polyolefin resin.
- A polyolefin resin powder prepared by the method according to any one of claims 1 to 13, which is characterized in that the powder particles are spherical and/or spheroidal, and have a particle size of 25-150 Āµm, and a particle size distribution D10 = 43-69 Āµm, D50 = 61-103 Āµm, and D90 = 85-138 Āµm.
- A selective laser sintering method, in which a polyolefin resin powder prepared by the method according to any one of claims 1 to 13 is used as a powder raw material for sintering.
- Use of a polyolefin resin powder prepared by the method according to any one of claims 1 to 13 in a method of manufacturing a three-dimensional object, in particular a method in which a three-dimensional object is manufactured using selective laser sintering.
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CN201510665024.3A CN106589418A (en) | 2015-10-13 | 2015-10-13 | Polypropylene resin powder for selective laser sintering as well as preparation method and application thereof |
CN201510750235.7A CN106674550A (en) | 2015-11-06 | 2015-11-06 | Polyethylene resin powder used for selective laser sintering and preparation method and application thereof |
PCT/CN2016/079396 WO2017063351A1 (en) | 2015-10-13 | 2016-04-15 | Polyolefin resin powder for selective laser sintering and preparation method therefor |
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US (1) | US10920025B2 (en) |
EP (1) | EP3363849B1 (en) |
JP (1) | JP6903052B2 (en) |
ES (1) | ES2794673T3 (en) |
WO (1) | WO2017063351A1 (en) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2020049020A3 (en) * | 2018-09-04 | 2020-05-14 | Karl Leibinger Medizintechnik Gmbh & Co. Kg | Laser-sintered filter, method for producing the filter, and method for ensuring fluid flow |
WO2020164728A1 (en) * | 2019-02-15 | 2020-08-20 | Robert Bosch Gmbh | Particles for selective laser sintering, process of producing the particles and their use |
DE102020119683A1 (en) | 2020-06-25 | 2021-12-30 | Rehau Ag + Co | Process for manufacturing a component using additive manufacturing |
RU2816001C1 (en) * | 2022-09-30 | 2024-03-25 | ŠŃŠ±Š»ŠøŃŠ½Š¾Šµ Š°ŠŗŃŠøŠ¾Š½ŠµŃŠ½Š¾Šµ Š¾Š±ŃŠµŃŃŠ²Š¾ "Š”ŠŠŠ£Š Š„Š¾Š»Š“ŠøŠ½Š³" | Polypropylene composition for producing articles by 3d printing, method for production thereof, use thereof and article made therefrom |
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JP6903052B2 (en) | 2021-07-14 |
JP2018534398A (en) | 2018-11-22 |
WO2017063351A1 (en) | 2017-04-20 |
US10920025B2 (en) | 2021-02-16 |
EP3363849B1 (en) | 2020-04-29 |
ES2794673T3 (en) | 2020-11-18 |
US20180355122A1 (en) | 2018-12-13 |
EP3363849A4 (en) | 2019-06-26 |
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